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Crucial influence of the intramolecular hydrogen bond on the coordination mode of RC(S)NHP(S)(OiPr)2 in homoleptic complexes with Ni II

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Babashkina, M.G. [UCL] Safin, Damir [UCL] Srebro, M. [University of Wroclaw (Poland)] Kubisiak, P. [University of Wroclaw (Poland)] Mitoraj, M.P. [University of Wroclaw (Poland)] Garcia, Yann [UCL]

Reaction of the deprotonated N-thiophosphorylated thioureas RC(S)NHP(S)(OiPr)2 [R = EtNH (HLI), iPrNH (HL II), Et2N (HLIII), 2,5-Me2C 6H3NH (HLIV), 4-Me2NC 6H4NH (HLV)] with NiII leads to complexes of the formula [NiLI-V 2]. The molecular structures of the complexes in the solid were elucidated by single-crystal X-ray diffraction analysis. In the complexes, the metal atom is found to be in a square-planar trans-N2S2 ([NiLII,IV 2]) environment formed by the C=S sulfur atoms and the P-N nitrogen atoms, or in a square-planar trans-S2S′2 ([NiL I,III 2]) environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands. Reaction of deprotonated N-thiophosphorylated thiourea HLV with NiCl2 leads to violet [Ni(L-1,3-N,S)2] or dark violet [Ni(L-1,5-S,S′) 2]·(CH3)2C=O crystals that were isolated by recrystallization from a mixture of CH2Cl2 or acetone, respectively, and n-hexane. DFT calculations confirmed that the [Ni(L I,II,IV,V-N,S)2] conformers are more stable (by 5-7 kcal/mol) than [Ni(LI,II,IV,V-S,S′)2], whereas [Ni(LIII-N,S)2] is less stable (by 7-9 kcal/mol) than [Ni(LIII-S,S′)2]. The main reason for higher stability of the 1,3-N,S versus 1,5-S,S′ isomers is the formation of intramolecular N-H⋯S=P hydrogen bonds. The same hydrogen bonds are impossible in complex [NiLIII 2]. In solution, complex [NiLIII 2] has revealed an exclusively 1,5-S,S′ coordination, whereas compounds [NiLI,II,IV,V 2] reveal at least two isomers in the 1H and 31P{1H} NMR spectra. The major species is assigned to the 1,3-N,S-coordinated isomer, and the minor signals are assigned to the 1,5-S,S′ isomer, which was confirmed by UV/Vis spectroscopic results. The electrochemical measurements reveal reversible one-electron reduction and irreversible oxidations both assigned to ligand-centred processes. Ligand-based oxidation processes agree well with TD-DFT results. Reaction of deprotonated RC(S)NHP(S)(OiPr)2 [R = EtNH (HLI), iPrNH (HLII), Et2N (HLIII), 2,5-Me2C6H3NH (HLIV), 4-Me 2NC6H4NH (HLV)] with NiII leads to [NiLI-V 2]. The metal atom is found to be in a square-planar trans-N2S2 ([NiLII,IV 2]) or in a square-planar trans-S2S′2 ([NiLI,III 2]) environment. Reaction of LV with NiII leads to [Ni(L-1,3-N,S)2] or [Ni(L-1,5-S,S′) 2]·(CH3)2C=O crystals. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Document type Article de périodique (Journal article) – Article de recherche
Access type Accès restreint
Publication date 2013
Language Anglais
Journal information "European Journal of Inorganic Chemistry" - Vol. --, no.4, p. 545-555 (2013)
Peer reviewed yes
Publisher Wiley-VCH Verlag
issn 1434-1948
Publication status Publié
Affiliation UCL - SST/IMCN/MOST - Molecules, Solids and Reactivity
Keywords Coordination modes ; Density functional calculations ; Nickel ; Thioureas ; X-ray diffraction
Links
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Bibliographic reference Babashkina, M.G. ; Safin, Damir ; Srebro, M. ; Kubisiak, P. ; Mitoraj, M.P. ; et. al. Crucial influence of the intramolecular hydrogen bond on the coordination mode of RC(S)NHP(S)(OiPr)2 in homoleptic complexes with Ni II . In: European Journal of Inorganic Chemistry, Vol. --, no.4, p. 545-555 (2013)
Permanent URL http://hdl.handle.net/2078.1/125609